Humous product



March 1943. A E. F. GRETHER 2,313,434

HUMOUS PRODUCT t I Original Filed May 10, 1939 HUMOUS MATERIAL SUCH AS MUGK ADDITION OF WATER,

ANIRONCOMPOUND AND AN ALKALI BASE IF NE EssARYf A ANAERoBIc FERMENTATION IN PRESENCE OF SOLUBLE IRoN HUMATE AND ALKALI BASE MANURE'LIKE HUMOUS PRODUCT CONTAINING HIGH BACTERIAL COUNT AND COMPOUNDS HAVING V NUTRIENT AND STIMULATING VALUES v R W terial also undergoes a slow decomposition which vention embraces broadly the concept of pro- Patented Mar. 9, 1943 1 5 a v HUMOUS rnonnc'r Ernest F. Grether, Midland, Micln, assignor to The Dow Chemical Company, Midland, Mich, a corporation of Michigan Continuation of application Serial lilo. 272,8 96, May10, 1939. This application March 16, 1940, Serial No. 324,519 I '5 Claims. '(CI. 71-16) My invention relates to a fermented humous Still another object of my lnventionis to promaterial, and more especiallylto a humous mavide a humous product containing soluble iron terial having manure-like properties. This ap- .humates and soluble alkali compounds. pilcation is a continuation or my co-pending Yet-another object of my invention is to pro-:

application Serial No. 272,896,]filed May 10, 1939. 5 vide ahumous product having many of the It is well known that humous material, such characteristics and containing many of the comas compost ceilulosic material and naturally 00- v pounds present in manure. curring humous material suchas muck; is bene- Afurther Obje t o y invention is to P ficial when applied to certain types of soil. This ahumous product which'is neutral or alkalinefin is'principally due to the factthat the moisture character, has manure-like characteristics, a high absorbing properties of the humous material asbacterial count, and plant stimulating value sists the soil-in retaining its moisture content, over and above the effect that would normally thereby providing soil-conditions in whichbacbe produced fromtheavailable plant food presteria beneficial to plant growth may multiply. ent.

After application tothe soil, this humous ma l5 With these and other objects in view, my 111'- makes available to the growing plants some of vidmg a humous product having manure-like the insoluble nitrogenous, proteinlc and other characteristics by subjecting a humous material compounds which have nutritive values. This to an anaerobic fermentation in the presence of decomposition is hastened if the soil is alkaline an iron compound and an alkali base or a'mixdue to the presence of lime. tureof alkali bases. A sumcient quantity of al- Hitherto, many attempts have been made to kali base is added to produce a hydrogen ion devise methods of treating these humous mate! concentration of at least 7,- and in the preferred rials so as to convert, the nutrient compounds f m f m invention the hydr n ion conc nwhichthey contain into a plant .available form tration of the mixture is controlled by the addibefore the humous material is applied to the soil. tion, if necessary, of additional quantities of the For example, in the autoclave-processv the humous alkali ibas during fermentation. The desiredv material is superheated to cause the conversion anaerobic fermentation is secured by the addiof some of these compounds. Other methods tion of 'sufilcient water to form a paste-like mass have been devised in which the material is subwhich will exclude the atmosphere, or by any jected to a fermentation which is usually of the other suitable method. aerobic or aerobic-anaerobic type. Various com- The Starting material to produce y invention pounds are sometimes added either befo e or is a humous material, that is, a substance that after fermentation to supply deficiencies in, the has e me a DYEViOuS fermentation, s ch as plant available contents of the humous material 5 Pe tm h i nite, leaf mold, or comp and to produce a'balanced fertilizer. a lulosic material such as decayed straw, as dis- Although the desirability of producing a hutlnguished from raw 'cellulosic materials, such as mous material having plant stimulating and Ier- CO S- W e y Product may be p oduced tilizing values is apparent, none of the above *1'1'01'11 any of the above mentioned types of hudescribed methods have produced a product 40 mous material, for purposes of illustration I which has met with any degree of commercial l disclose-the prod as it s produced when success, and -it, is therefore obvious that these m k used as a i materia' and ch efforts to make available the plant nutrients is e y d o pr mote the anaerobic fermentacontained in humous material have been wholly tion. or partly unsuccessful. Moreover, none of the Muck is a naturally Occurring humous maprior methods produce an end product having terifll w h has undergone a previou fermenthe manure-like properties and bacterial count tion, is usually acidic in chara ter, and

which distinguish th applicant's t, I possesses a low bacterial count. However, either One of the objectsof my invention is to proan acidic- IIBMIBJ or alk in k m y e used vide a product having an increased bacterial a a starting material in my Pr es unless the count and a. decreased number of types of bacalkalinity f h substance is .5 to th presence teria as compared to the humousmaterial from of o p nds c ntaining calcium, such as limem h 1t 1 d stone or the alkaline earth metals. Mucks from .Another object of my invention is to provide a many alkaline bogs owe their l n y t0 h humous product containing a plant stimulant. Presence of these compounds and cannot be utilized in my process for reasons which will be subsequently disclosed.

The single sheet of drawings discloses a flow sheet illustrative of one form of my invention.

In the illustrated method of producing the desired end product, a naturally occurring humous material, such as muck, is used asthe starting 1 material. 'In carrying out the process, a quantity of water, unless the selected material already contains sufllcient water to be in the form of a paste, and, if necessary, an ionizable iron compound and an alkali base or a mixture of alkali bases are added to the selected humous material.

Preferably, I add the ionizable iron compound' 5 before the alkali base, although this order may be reversed if desired. If either-the ironcompound or alkali base is present inthe' start ing material in sufficient quantities for the purposes of is process, additionalv amounts need not be added. The ionizable iron compound and baseare preferably added inthe form of aqueous solutions. i

The quantityof water added varies with moisture content of the original starting material and the amountof' water added in the ionizable iron compound and the alkali "base solutions.

However, the resulting mixture, when these substances have been added, should have a sufllcient moisture content to form a liquid paste-like'mass.

I'have found that normally, in] order to obtain this jliquidpaste-like form, the moisture content must be at 'least'seventy percentby weight of the original humous starting material.

Among the various iron compounds which can be used may be mentioned ferric or ferrous hydroxide, ferric'or ferrous sulfate, ferric chloride, ferrous ammonium. sulfate,or amixture of these preparing iron humate which comprises first preparing or separating the humic acid in purifled condition, dissolving the acid in an aqueous alkali, and then adding a soluble iron salt, there- 'present.' Moreover, the alkali apparently releasefs some of the compounds, such as protein, which are present in the humous material, thus making them available for bacterial food and or similar; "compounds, such as iron acetate, 'or' citrate. The proportion of iron compound 'employed varies widely 'withthe quantity of iron present, in the original starting material and in theft'ype of "materialzlselected. Muck usually contains a quantity of insoluble iron humate, and

if sufficient off. this" or any other iron compound is present, nofa dclitlonal iron is" necessary; In

practice, when an average. type muck is em-' ployed,'thequantity'of iron added varies between 0.05 a.n('i().5."grarn"atom ofiron per kilogram of dry humous material; Inbr'der to enable. the iron to be thoroughly mixed with the humous materiaI -itis preferably added in the form of an aqueoussolution. The concentration of solution used dependsupon the physical condition of thestarting'material towhich it is added.

'After'the ironcompound has been added, a

suilicient quantity. of an alkali base, such asthe hydroxides or carbonates of, potassium, sodium, or ammonia, or a mixture of these'baseais added to' the humous material to cause a'hydrogen' ion' concentrationin theres'ulting mixture of from '7 to 10, and preferably'fbet'ween 8"'and '9.' The proper regulation of'this pHvalue is important as it results in a morecomplet'e' 'conversion of the starting material.

Of course, ifa sunicient quantity "of these alkali bases'is already present'in the material, it

will be unnecessary to add an additonal amount. The alkali base, if necessary, is preferably [added inthe form of an ,aqueouslsolution so that maybe readily mixed with thehumous material. The addition of the alkal Bade to the humous material causes the iron compoundj'to be dis-' solved with the formation of a solublei humate iron within the mass. This novel'reaction requires less alkali than the known method for thereby initiating a fermentation.

The alkali employed also reacts to form salts which are retained in the .fertilizer product butwhich do not interfere with the iron humate. For thisreason an alkali, such as the compounds of ammonia or potassium, which add food value to the product, is preferably employed, although the compounds of sodium may be employed if desired.- The alkali earth metal hydroxides, particularly lime, cannot satisfactorily be ,used since they render humate iron insoluble and unavailable to plants.

The applicant has found that the presence of a sufficient quantity of iron humate and an al= kali base are absolutely'necessary in practicing hisprocess. The presence of these compounds in soluble form is the determining factor in producing during the anaerobic fermentation, the large increase in bacteria and the resulting manure-like end product containing-plant stimu-' lants.

After a suflicient quantity of an alkali base has been added to the humous material to form the soluble iron humate and'to produce a hydrogen ion'concentration'of from 7 to 10, the resulting mixture is subjected to an anaerobic fermenta-- tion'of from a few'days to three months duration at room temperature or at a temperature which is regulated at any desired point in. a range between 20 and 40 C. In this connection the applicant has found that, if temperatures above 40 C., are employed, the desired increase in bac-' terial growth of the type desired cannot be obtained except with great dimculty, and that bacterial growth ceases above 50 C. An additional amount of the alkali base may be added from time to time during the fermentation,-if necessary, to maintain the proper pH value.

By-the term anaerobicfermentation in this application is meant a fermentation which is truly anaerobic as'distinguishe'd from the aerobic-anaerobic fe'rmentations usually'disclosed in the prior art: The most j-convenient way of pro ducing true anaerobic conditions is to reduce the humous-material to a paste-like mass which will practically exclude the penetration of the atmosphereinto the interior of themixture during,

fermentation.

These conditions were ing-the original fermentation of the cellulosic materials which form the "humous -material known 'asmuck, although even muck. situated on lake bottoms may decay under more or less aerobic conditions since air can penetrate into water, while the penetration of the liquid paste-like form of the materialin my process is much-more sometimes present durnitrifying type.

limited due to the consistency of thematerial. This type of .fermentationis entirely different from a fermentation of a humous material having a lowermoisturecontent.

While the reduction of the humous material to apasteis a practical method of conducting the fermentation, it is obvious that other means of excluding the atmosphere during the fermentation could be devised. Such means would come within the scope of this invention. The applicant has notbeen able to ascertain the exact type of bacteria which is developed in his process, although it is apparently not of a The humous'material is selfinoculated by bacteria in the air, which isbelieved to be a soil type of bacteria. Of course,

many types ofbacteria are present at first, butthe condition of the humous material produced by the process is such that the desired type or types of bacteria multiply at the expense of those not desirable, and therefore the desired endeffect upon growing plants, the increased bac terial count and the presence of the soluble iron humate during the anaerobic fermentation results'in an end product having a distinct manure-like odor.

In this connection, that, while'the bacterial count reaches apeak during the first week of the fermentation, the

manure-like odor is usually more pronounced after a fermentation of three weeks. Moreover, the material is at least as active'if the fermen tationis continued for-from two to three months.

The bacterial action breaks-up the organic material, especially the-nitrogenous materials, andconverts them into products of a-nature similarto that produced by intestinal digestion and the following manure fermentation; The manurelike odor is characteristic of the fermentation and is entirely unlike the putrefactive' odor usually associated with the fermentation of organic materials in the presence of oxygen. n the contrary, 'it resembles. the odor of manure,

especially stored liquid manure.

This odor is the result of the presence of ammoniumisulfide, skatole and indole derivatives, suchas are found in manure. Theodor su gests that the fermentation causes a reaction in which :the cystine radical is split from the molecule :of theproteinic material which forms a part of the contents of the humous material. This reaction reduces the sulfur to hydrogen sulfide andauses a corresponding oxidation of other ingredients. The hydrogen sulfide reacts with ammonia to form ammonium sulfide. As cystine is toxic to plants, this reaction is beneficial. When this reaction of one part of the molecule occurs, it is believed that other parts of the molecule are broken up into amines. amino acids and amino alcohols. It is probable that the bacteria use these compounds partly for food and aid in converting other ingredients into other forms.

the applicant has found action resultsina. larger consumption .of i min-.

eral elements and carbondioxide by the plants.-

In this connection it should also be noted that,

bacteria are very noticeable upon This bacterial action in the presence of soluble iron humate produces the stimulant content of the processed material. Thatsuch stimulants are present is indicated-inpart by the effect of.

the end product of the process on growing plants. This effect is very similar to that produced by rotted manure. The end product is a fertilizer because itcontains plant food constituents. ,It also contains a plant stimulant because its grow-. ing' action on plants is in excess of the food content. The bacteria contained in this humous end product'is believed to be partly-responsible for this plant 'stimulant action, because their presence renders :soil minerals moreavailable, but it is also believed that the stimulating substanceswhich are releasedfrom' the nitrogenous,

proteinic,$ol other materials, through their ac.- tion increases the appetite of the plant. IThis when the end product of the processissubjected to heat .for sometime and cooled and then-.ex-- tracted with ether, the ether extract contains methyl butyric acid. Methyl butyric acid is also obtained when auxin is decomposed. 'Auxin hetero-auxin and skatole can be obtained from manure and therefore,=my end product must contain these ingredients or similar ones which have a stimulating action on plants. 1

The product produced by the'fermentation is a dark brown paste which may be stored safely or applied directly to the soil. -Applicati0ns of this material. have been found toincrease the growth and yield of' plants and cause early mae 'turing.- Moreover, the'sugar, protein andvita min contents of the plants appear to be in.- creased. When fruits, such as strawberries, ;are

grown, the taste is improved. The product contains from 30 to 40 percent by weight of'dry material and is usually neutralor alkalinein reaction; If'the material is to be used on soil of basic reaction, the pH concentration of this material may be reduced by adding. an acid,min-, eral fertilizer; A marked increasein the num-.

ber of bacteria and a decrease in the types of examination.

'If desired, this end product may tion of some of the humous materiallwhich was employed as. a starting material in theprocessu. However, if-desired, a material such as dried peat, bran or other cellulosic material having water absorption powers may be used. Sumcient 3 dry material is addedto provide an. end product having a dry content of from 60 to .80 percent. by weight. There is no danger of destroying the abundant bacterial life by following this procedure-which might result if an attempt were made to dry the productby ordinary methods.

The resulting product somewhat porousand has a tendency to crumble as distinguished from' the imporous, heavy and dense untreated endproduct.

The following gives a specific example to illustrate one method of producing the end product which forms the basis of this invention, it being understood that other starting materials may be used and that the quantities and types of substances added to the starting material men-' tioned in the example may be varied. The length of fermentation depends upon the conditions I microscopic be mixed with ,a filler, such as disclosed in my co-pending application Serial No. 204,475, which was filed April" I '26, 1938. Preferably, thisjfiller is-a dried por pr sent and thetype oi material w ich s sole'cted'as the starting material for. the process.

\ --1200-grams of peat was treated with a soul-' tion of 130 grams of potassium hydroxide in 3480 cubic centimeters of water, "after .which80 grams of anhydrous ferric sulfate was added with stirring. The resultant mixture was a slightly acid paste-like mass comprising humateiron and potassium salts as well as nitrogen compounds initialiypresent ln'the peat. --It was neutralized with cubicc'entimeters'of 1 normal aqueous" potassium hydroxide solution after whichit was fermented by standing in moist condition attemperatures between and C. :After standing underrsaid condition for. 3 days the'product had developeda manure-like odor 'which became more intense on longer standing. The fermented product was highly eflectiveas a-fertilizer and plant stimulant.

If'd'esired; 1200 grams of dried peat may be.

addedto thismaterial. 'If thelmoisture content ofthe resultinamassis still too high, it may be exposed to air drying until the moisture content kaline in character, as previously mentioned, but

cannot contain an appreciable amount of the alkaline earth metal hydroxides or other insoluble compounds containinggthe calcium ion. None. of the substances-mentioned need be added to-the process ii they are already present in sufllcient quantity in the original humous startingmaterial, and all of the water maybe added in the form. of a solution containing the iron compound or-the alkali base; or both, the sole limitation in'the process being that an anaerobic fermentation of the type. described be conducted in the presence-of-suflicient .quanti. ties of soluble iron .humate and an alkali base or mixture of bases.

While I have described the manure-like characteristics-of my novel composition, it is be lieved obvious that .humous productscontaini c ess n y t e same en ral characteristicsmaybe produced without departing from. the.

broad concept of this invention... I therefore in-.

tendthat this application be only limited by the. priorart and the scope ofthe appended claims,

to 1.0 andwhichcontains plant available nutrients and plant stimulants, a marked increase in the numberot bacteria. and a marked decrease in thetypes ot bacteriawhich were present in Y the originalhumous material.

.2. A new composition of matter comprising a manure-like humous material in theiorm of a relatively porous material which contains from 20 to 40 percent water which has been formed by iermentinz under substantially anaerobic conditionsand in the presence of soluble iron humate and a suiiicient amount of an alkali base to ive h mixture a pH of from 7 to 10, a humous material in which sui'llcient water is present (to form a paste-like mass, and then adding asudlcient quantity of dry cellulosic ma,- terial to reduce this moisture content. said composition containin: plant available nutrients and plant stimulants. a marked increase in the numbet or bacteria. and a marked decrease in the types or bacteria which. were present in the by fermenting. under substantially anaerobic conditions and in the presence oi soluble iron humate and a suiilcient amount or an alkali base to give the mixture at pH of from 8 to 9. a humous material in which sufllcient water is present to ly 70 percent by weight of water, said compo-l sition having been fermentedunder substantially anaerobic conditionsin the presence of soluble iron humate and a sufllcient amount of. an alkali form a pastedike mass, and then adding a'sumcient quantity or dry ceilulosic materialto reduce this moisture content, said composition containincplant available nutrients and plant timulantaia marked increase in the number at bacteria, and a marked decrease in the type of bacteria which were present in the original humous material. Y

A composition comprising a, heavy, dense, and substantially non-porous manuredike material having a. pronounced manure-like odor. which manure-like material is prepared by the fermentation under. substantially anaerobic conditions of Immune material at temperatures.

between about 29 andebout 40 C. in the presence of soluble iron .humate in amount correspondingito at least 0.05 gram-atom oi iron per kilogram dry weight 01 the humans material. and in the presencev oi suflicient alkali .soythat the pH value of the mixture is between 7 and 10, and sufficient water to form. athick paste oi themixture. I

5. A composition comprising a heavy. dense nd substantially non-porous manure-like product which when ireshly prepared po se ses a pronounced manure-like odor. and which product is prepared by the fermentation of humous. material under substantially anaerobic condi- -tions at about room temperature in the presence of soluble iron hurnate. sufilcient alkali so that the pH value. oi the mixture is between 7 and 10-- and. sufllclent waterto term a thick paste oi the mixture. I

. .ERNES'IEGRE'I'HER... 

